Water-insoluble phenyl-azo-phenyl dyestuffs

ABSTRACT

SAID DYESTUFFS BEING HIGHLY SUITABLE FOR THE DYEING OF FIBROUS MATERIALS CONSISTING OF CELLULOSE-2 1/2 -ACETATE, CELLULOSETRIACETATE, POLYAMIDE, POLYURETHANE OR, PARTICULARLY, OF POLYESTERS, SUCH AS POLYETHYLENEGLYCOLTEREPHTHALATES.   Water-insoluble monoazo-dyestuffs of the formula

WATER-ENSOLUBLE PHENYL-AZO- PHENYL DYESTUFFS Inventors: Erich Brenneisen, l-lofheim/Taunus; Helmut Lindner, Frankfurt/Main; Heinz Schmidt, Kelkheim/Taunus, all of Germany Farbwerke Hoechst Alrtiengesellschait varmals Meister Lucius 8: Bruning, Frankfurt/Main, Germany Filed: Nov. 13, 1968 Appl. N0.: 775,515

Assignee:

Foreign Application Priority Data Nov. 28, 1967 Germany ..P 16 44 234.5

US. Cl ..260/207.l, 8/41 C, 8/50 Int. Cl. ..C07c 107/06, C09b 29/08 Field of Search ..260/207, 207.1

References Cited UNITED STATES PATENTS 3/1937 Muller ..260/207 51 Feb. 20, 1973 4/1939 Felix et al ..260/207 10/1939 Felix et al. ..260/207 X Primary Examiner-Lewis Gotts Assistant Examiner-C. F. Warren Att0meyCurtis, Morris & Safford [57] ABSTRACT Water-insoluble monoazo-dyestuffs of the formula I 13 NH 1 CO-CH3 5 Claims, No Drawings WATER-INSOLUBLE PHENYL-AZO-HHENYL DYESTUFFS The present invention relates to new water-insoluble monoazo dyestuffs corresponding to the general formula(l) wherein D represents the radical of a diazo component of the benzene series being free from groups imparting solubility in water, and to a process for preparing these dyestufis, wherein aromatic amines of the general formula (ll) D Nl-i II, in which D is defined as above are diazotized and combined with a coupling component of the formula (III) The benzene nucleus of the diazo component may carry groups which do not impart solubility in water, for example, nitro, cyano, trifluoromethyl, alkylsulfonyl, acetyl and/or carboxylic acid ester groups or chlorine and/or bromine atoms.

The coupling component used in the instant process corresponding to the general formula 111 can, for example, be prepared by the process described in J. Chem. Soc. (London), Volume of 1948 pages 1228-1229.

Amines from which the diazonium compounds used in the invention may be formed are, for example, the following: 4-nitroaniline, 2-ch1oro-4-nitroaniline, 2- bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2,4- dinitroaniline, 4-cyano-2-nitroaniline, 3-nitro-4-aminobenzotrifiuoride, 5-nitro-2-amino-benzotrifluoride, 5- nitro-2-amino-benzoic acid methyl ester, 2,6-dichloro- 4-nitroaniline, 2,6-dibromo-4-nitroaniline, 6-chloro- 2,4-dinitroaniline, 6-bromo-2,4-dinitroaniline, 4- aminoacetophenone or (2-amino-5-nitrophenyl)- methylsulfonyl.

The coupling normally proceeds in an acidic to neutral medium to which acid-binding agents, such as sodium acetate or magnesium carbonate, may advantageously be added. The dystuffs, which are obtained in a water-insoluble form are, for example, separated by filtration and washed with water until free from the adhering electrolytes.

The new water-insoluble monoazo dyestuffs of the invention are processed by known methods with use of dispersing agents into dyeing compositions. These preparations yield at a very good ratio of dyestuff concentration employed to tinctorial strength obtained, on synthetic fibers, such for example, as cellulose triacetate, cellulose-2 rfi-acetate, polyamides or polyurethanes, in particular, however, on polyester fibers,

for example, polyethyleneglycol terephthalate, dyeings and prints distinguished besides a high intensity of coloration by a very good processing and application fastness, especially to light, wet processing and action of heat.

For dyeing polyester materials the new dyestuff are conveniently used in the form of the above-mentioned dyeing compositions either as powders or granules or suspensions capable of being poured. They are applied from an aqueous bath at temperatures above C at a pressure or in the presence of known carriers at about 100C. Another method providing intense shades consists in impregnating tissues or knit fabrics made of polyesters with suspensions of the new dyestuffs, drying and subsequently exposing to a short heat treatment, for example at a temperature between 190 and 210C. Furthermore, the dyestuffs are highly appropriate for dyeing blends of fibers containing a portion of polyesters. In dyeing blends of polyesters and wool with a good color yield on the polyesters the wool portion is only faintly colored, so that the wool coloration can be easily removed by an additional treatment with reducing agents or emulsifiers.

The following Examples are to illustrate the invention but they are not intended to limit it thereto, the

parts and percentages being by weight unless otherwise stated.

EXAMPLE 1 Seven parts of anhydrous finely pulverized sodium nitrite were introduced at 60C into parts of sulfuric acid of 96 percent strength. The resulting nitrosylsulfuric acid solution was, subsequently, cooled to 05 C at which temperature 16.3 parts of 2-cyano-4- nitroaniline were added and then stirred for 4 hours at 5C.

The so prepared diazonium salt solution was run into a mixture consisting of 202 parts of ice, 202 parts of water and 1 part of amidosulfonic acid of 100 percent strength, to be poured, subsequently, into a solution of 23.3 parts of 3-acetoaminodiphenylamine of 100 percent strength and 200 parts of 99 percent glacial acetic acid. By addition of sodium acetate of 100 percent strength the pH value was adjusted to 4. The violet dyestuff which precipitated yielded, when applied on polyester fibers from an aqueous dispersion, dyeings very fast to light and thermofixation.

EXAMPLE 2 18.3 parts of 2.4-dinitroaniline were mixed with 158 parts of acetic acid of 99 percent strength and diazotized while stirred at 15C with 32.3 parts of nitrosylsulfuric acid of 40 percent strength. 23.3 parts of 3-acetoamino diphenylamine in 250 parts of acetic acid of 99 percent strength containing as admixture 1 part of amidosulfonic acid of 100 percent strength were placed into the coupling vessel. To the said solution, adjusted with solid sodium acetate to a pH of 4 5, the diazonium salt solution was added dropwise with stirring within about half an hour, the temperature of 0 3C being maintained by adding ice. Thereafter, it was stirred on for one hour. The obtained dyestuff dyed polyester fibers violet shades very fast to light and thermofixation.

EXAMPLE 3 2. The water-insoluble monoazo-dyestuff of the fori 20.7 parts of 2.6-dichloro-4-nitroaniline were mula diazotized as disclosed in Example 2. Thereafter, the diazonium'salt solution was poured within half an hour N 02 with stirring into a solution of 23.3 parts of 3- acetaminodiphenylamine in 250 partsvof acetic acid of 99 percent strength adjusted by means of solid sodium I acetate to a pH between 4 and 5' that contained in ad- NH-C o-CH;

mixture 1 part of amidosulfonic acid of 100 percent strength. During the coupling the temperature was kept between 0 and 3C by addition of ice. The whole was 3 The watepi l bl t ff f th f stirred for i to 2 hours, the dyestuff which had mul'a u e yes precipitated was separated by filtration, washed with water and dried. The so obtained dyestuff showed a red coloration and when applied on polyester fibers from 01 an aqueous dispersion yielded dyeings of outstanding fastness to light and thermofixation. O2N N=NNH The following table contains further examples of A: dyestuffs obtainable by diazotization of the amines feal NHTCOTCH. tured in column 2 and their coupling with 3- acetaminodiphenylamine. The fourth column lists the tints produced with these dyestuffs on 4. The water-insoluble monoazo-dyestuff of the forpolyethyleneglycolterephthalate fiber materials. mula No. Diazo component Azo component Shade 1 2'chloro4nitroam'line 3 acetoaminodiphenylamine Bluish red.

2 fi-chloro-3-nitroaniline ..do Reddish orange. 3 Myano-Z-nitroaniline ..do... Bluish red.

5. fi-nitro-Zaminobenzotrifluoride Bluish red.

6- E-nitro-Z-aminobenzoie acid methyl ester Do.

7. 2,6-dibromo-4-nitroaniline Do.

9 6-bromo-2,4-dlnitroaniline- Do.

10 4aminoacetophenone Scarlet.

11 (5-nitro-2-amino-phenyDmethyl-sultone do Violet.

What is claimed is:

Br 1. A water-insoluble monoazo-dyestuff of the formu- A NHC 0-CH3 l 5. The water-insoluble monoazo-dyestuff of the formula 0-011: 5

in which A represents hydrogen, chlorine, bromine, Cl nitro, trifluoromethyl, lower alkylsulfonyl or a carboxylic acid lower alkyl ester group, B represents hydrogen, chlorine or bromine, and C represents nitro, I IH-C 0CH: trifluoromethyl or acetyl. 

1. A water-insoluble monoazo-dyestuff of the formula
 2. The water-insoluble monoazo-dyestuff of the formula
 3. The water-insoluble monoazo-dyestuff of the formula
 4. The water-insoluble monoazo-dyestuff of the formula 